Strategies to control the size, shape, and lattice arrangement, introduce doping agents, and induce heterostructuring in electrocatalysts are strongly desirable to tailor their activities. Herewith, a one‐pot strategy utilizing polyacryloyl hydrazide (PAHz) as the composition directing agent and metallic Ni surface as the shape directing agent is employed to grow Co3O4 doped NiCu alloy nanocuboids on Ni foam (NF) under hydrothermal conditions for electrocatalytic H2 production. The resulting bi‐functional electrodes are suitable for methanol oxidation reaction (MOR) coupled green H2 production with effective energy efficiency. The low overall potential (MOR+HER) of 1.78 V to realize the current density (j) value of 100 mA cm−2 and extended durability (100 h@10 mA cm−2) along with the selective conversion of methanol to formate support the viability of the NF‐PAHz‐Co3O4@NiCu for the said operation. The electrode also displays efficacy toward oxygen evolution reaction (OER) activity and jOER value of 100 mA cm−2 is realized at a potential value of 1.65 VRHE with adequate durability. Overall, the synthetic strategy is general, scalable and may be extended to grow other metal oxide doped alloy nanostructures in the future.